CN107235868A - A kind of sulfide oxidation method - Google Patents

A kind of sulfide oxidation method Download PDF

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Publication number
CN107235868A
CN107235868A CN201610186585.XA CN201610186585A CN107235868A CN 107235868 A CN107235868 A CN 107235868A CN 201610186585 A CN201610186585 A CN 201610186585A CN 107235868 A CN107235868 A CN 107235868A
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titanium
hts
silicon
stage
weight
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CN107235868B (en
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史春风
林民
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of sulfide oxidation method, including：Step (1 1), by the tert-butyl alcohol and oxygen haptoreaction, catalytic condition causes the content of TBHP in the reactant mixture that haptoreaction is obtained to be more than 1 weight %；Optional step (1 2), the reactant mixture that step (1 1) is obtained is mixed with inorganic acid；Step (2), under conditions of being enough sulfide oxidation, the reactant mixture and the raw mixture of thioether and HTS haptoreaction that will be obtained containing step (1 1), or the mixture and the raw mixture of thioether and HTS haptoreaction that will be obtained containing step (1 2).This method can obtain higher device effective treating capacity, and can obtain higher thioether rate and desirable oxidation selectivity of product.This method directly installs sulfide oxidation reaction unit additional at the material outlet end of existing Oxidation of t-Butanol device, it is easy to implement.

Description

A kind of sulfide oxidation method
Technical field
The present invention relates to a kind of sulfide oxidation method.
Background technology
Sulfoxides are important sulfur-containing compounds, and such as dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, It is colourless transparent liquid under normal temperature, with the characteristic such as highly polar, high-hygroscopicity, flammable and higher boiling be non-proton.Dimethyl Sulfoxide is dissolved in water, ethanol, acetone, ether and chloroform, is the strong atent solvent of polarity, is widely used as solvent and reaction is tried Agent.Also, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, it can be used as the extraction that alkane separates with aromatic hydrocarbon molten Agent, for example：Dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or butadiene, and process solvent is used as in acrylonitrile polymerization reaction With the solvent that reels off raw silk from cocoons, as the synthetic and the solvent that reels off raw silk from cocoons of polyurethane, as polyamide, fluoroaluminate glasses, polyimides and The synthetic of polysulfones.Meanwhile, in medical industry, dimethyl sulfoxide (DMSO) not only can directly as some drugses raw material And carrier, and the effect such as anti-inflammatory analgetic, diuresis, calmness can also be played, therefore frequently as the active component of analgesic drug product Make an addition in medicine.In addition, dimethyl sulfoxide (DMSO) can also be extracted as capacitor dielectric, antifreezing agent, brake fluid, rare metal Agent etc..
Sulfoxide type is typically prepared using sulfide oxidation method, according to the difference of used oxidant and mode of oxidizing, generally bag Include nitric acid oxidation method, peroxide oxidation method, Ozonation, anodizing and nitrogen dioxide oxidizing process.Nitric Acid Oxidation The deficiency that change method is present is that reaction is whard to control, and equipment corrosion is serious, while environmental pollution is heavier.Ozone oxidation rule There is the problem of dimethyl sulfide conversion ratio is low.Anodizing is unsuitable for extensive implementation.Nitrogen dioxide oxidation rule is deposited The problem of environmental pollution.
The reaction condition of peroxide oxidation method is gentle, and equipment and process route are simple, and product does not need alkali to be neutralized, And it is substantially pollution-free to environment.But, as oxidant the most frequently used in peroxide oxidation method, hydrogen peroxide is usual There is provided in the form of hydrogen peroxide, its commodity concentration is general between 20-50 weight %, inevitable so in reaction system A large amount of water can be introduced, although water can play a part of solvent, as meltage of the thioether of reactant in water still It is so limited, in order to improve the meltage of thioether, the large usage quantity of water or need to use cooperatively organic solvent, this can not keep away Exempt to reduce the effective treating capacity of device.
The content of the invention
It is an object of the invention to provide a kind of method of oxidizing sulfur ether, this method need not additionally introduce solvent, result in Higher device effective treating capacity；This method can also obtain higher thioether rate and desirable oxidation selectivity of product simultaneously.
The invention provides a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step Suddenly (1-2)：
In step (1-1), by the tert-butyl alcohol and oxygen haptoreaction, the catalytic condition causes haptoreaction to obtain Reactant mixture in TBHP content be more than 1 weight %；
In step (1-2), the reactant mixture that step (1-1) is obtained is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reactant mixture that will be obtained containing step (1-1) With the raw mixture and HTS haptoreaction of thioether, or the mixture and sulphur that will be obtained containing step (1-2) The raw mixture of ether and HTS haptoreaction.
The method according to the invention, the quantity of solvent additionally introduced is low or even can not introduce, and resulting in higher device has Imitate treating capacity.Also, the method according to the invention can obtain higher thioether rate.Meanwhile, according to the side of the present invention Method can also obtain higher desirable oxidation selectivity of product.
The method according to the invention, the reactant mixture containing TBHP of Oxidation of t-Butanol formation is without separation Go out TBHP therein and can be used to step (2), on the one hand reduce the loss of material that separation process is caused, On the other hand technological process is simplified.During using the method for the present invention by sulfide oxidation, directly in existing Oxidation of t-Butanol The material outlet end of device installs sulfide oxidation reaction unit additional, it is easy to implement.
Embodiment
The invention provides a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step Suddenly (1-2)：
In step (1-1), by the tert-butyl alcohol and oxygen haptoreaction, the catalytic condition causes haptoreaction to obtain Reactant mixture in TBHP content be more than 1 weight %；
In step (1-2), the reactant mixture that step (1-1) is obtained is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reactant mixture that will be obtained containing step (1-1) With the raw mixture and HTS haptoreaction of thioether, or the mixture and sulphur that will be obtained containing step (1-2) The raw mixture of ether and HTS haptoreaction.
In the present invention, " optional " and " alternatively " represents inessential, it can be understood as " with or without ", " including Or do not include ".
In step (1-1), the tert-butyl alcohol and oxygen haptoreaction obtain Oxidation of t-Butanol containing TBHP Reactant mixture, the reactant mixture without carry out separation can directly as sulfide oxidation react oxidant use, And result in high thioether rate and desirable oxidation selectivity of product；Unreacted tertiary fourth in simultaneous reactions mixture Alcohol is either still respectively provided with certain dissolubility to thioether to desirable oxidation product, so as to slacken for extra solvent Demand, it is possible to increase the effective treating capacity of device.
In the method according to the invention, step (1-1), the reaction mixing that the catalytic condition is typically obtained The content of TBHP is more than 1 weight % in thing, such as 2-90 weight %, and the content of the tert-butyl alcohol is 99 weight % Hereinafter, such as 10-98 weight %.From the angle of the further effective treating capacity for improving device, step (1-1), The catalytic condition causes the content of TBHP in obtained reactant mixture to be preferably 10-70 weight %, more preferably 15-60 weight %, more preferably 20-50 weight %, particularly preferably 25-45 weight %；Uncle The content of butanol is preferably 30-90 weight %, more preferably more preferably 40-85 weight %, 50-80 weight %, Particularly preferably 55-75 weight %.
Tert-butyl hydroperoxide can be obtained by adjusting ratio and catalytic condition between the tert-butyl alcohol and oxygen The content of hydrogen meets the reactant mixture of above-mentioned requirements.Specifically, the mol ratio of the tert-butyl alcohol and oxygen can be 1：0.01-20, Preferably 1：0.1-10, more preferably 1：0.2-5, more preferably 1：1-4, particularly preferably 1：1.5-3.Institute Stating haptoreaction can be carried out at a temperature of 70-160 DEG C, carried out, more preferably existed preferably at a temperature of 90-140 DEG C Carried out at a temperature of 100-120 DEG C.Carry out pressure in the catalytic reactor can in the range of 0-3MPa, It is preferred that in the range of 0.5-2.5MPa, more preferably in the range of 1-2MPa, the pressure is in terms of gauge pressure.The present invention In, statement " ×-× in the range of " include two endpoint values.
In step (1-1), oxygen can use the oxygen of pure state, can also use oxygen-containing gas.The oxygen-containing gas one As contain oxygen and carrier gas, the carrier gas for example can be nitrogen and/or group 0 element gas (such as argon gas).It is described oxygen-containing The consumption of oxygen typically can be 0.1-99 volume %, more preferably preferably 50-95 volumes %, 80-90 volumes in gas %.The oxygen-containing gas can be the gaseous mixture by the way that pure oxygen and carrier gas are obtained by mixing, and also can directly use air.
In step (1-1), contact of the tert-butyl alcohol with oxygen is carried out preferably in the presence of at least one peroxide, described Peroxide plays a part of accelerator, can further improve reaction efficiency.Mole of the peroxide and the tert-butyl alcohol Than that can be 0.0001-0.1：1, preferably 0.0005-0.05：1, more preferably 0.001-0.04：1.The peroxide Refer to the compound for containing-O-O- keys in molecular structure, can be hydrogen peroxide and/or organic peroxide, organic mistake Oxide refer to one or both of hydrogen peroxide molecule structure hydrogen atom by organic group replace formed by material.It is described The instantiation of peroxide can include but is not limited to：Hydrogen peroxide, TBHP, ethylbenzene hydroperoxide, Cumyl hydroperoxide, Peracetic acid, Perpropionic Acid, cumyl peroxide, di-t-butyl peroxide, peroxidating two Benzoyl and dilauroyl peroxide.In the present invention, the organic peroxide is preferably R1-O-O-R2, R1And R2It is identical Or it is different, can be each H, C4-C12Straight or branched alkyl orR3For C4-C12Straight chain or branch Alkyl group, R1And R2It is asynchronously H.
The method according to the invention, step (1-2) is optional step, i.e.,：The reaction that step (1-1) can be obtained Mixture is sent directly into step (2) and thioether and HTS haptoreaction；Step (1-1) can also be obtained Reactant mixture feeding step (1-2) in mix with inorganic acid after, then the mixture feeding step that step (1-2) is obtained Suddenly in (2) with thioether and HTS haptoreaction.The reactant mixture that step (1-1) is obtained is sent directly into step Suddenly in (2), the operation terseness of the inventive method can be improved；The reactant mixture feeding that step (1-1) is obtained In step (1-2), the reactant mixture for then obtaining step (1-2) is sent into step (2), can further be carried The conversion ratio and the selectivity of desirable oxidation product of thioether in high step (2).It should be noted that regardless of whether being walked Suddenly (1-2), as the case may be, the reactant mixture that step (1-1) is obtained can be concentrated or diluted, with Meet the requirement of step (2).
In step (1-2), the tert-butyl group in the reactant mixture that the consumption of inorganic acid can be obtained according to step (1-1) The content of hydrogen peroxide is selected.Usually, tert-butyl group mistake in the reactant mixture that inorganic acid is obtained with step (1-1) The mol ratio of hydrogen oxide can be 0.00001-0.1：1, preferably 0.0001-0.05：1, more preferably 0.001-0.01：1.
From the further angle for improving thioether rate and desirable oxidation selectivity of product in step (2), step (1-1) The mixing of obtained reactant mixture and inorganic acid preferably 20-100 DEG C, more preferably 20-80 DEG C, further preferably exist Carried out at a temperature of 25-60 DEG C (such as 30-40 DEG C).Mixed in the reactant mixture for obtaining step (1-1) with inorganic acid When, the pressure in reactor mixed can be 0-2MPa, and preferably 0-0.5MPa, more preferably normal pressure are (i.e., 1 standard atmospheric pressure), the pressure is in terms of gauge pressure.The time of the mixing can be typically more than 0.1 hour, be preferably 0.1-5 hours, more preferably 0.5-4 hours (such as 2-4 hours).
The inorganic acid can be more than common various inorganic acids, such as one or both of halogen acids, sulfuric acid and phosphoric acid. Preferably, the inorganic acid is halogen acids, so resulted in step (2) the thioether rate that further improves and Desirable oxidation selectivity of product.It is highly preferred that the inorganic acid is HCl and/or HBr.The inorganic acid can be with water-soluble The form of liquid is provided, and the content of inorganic acid can be conventional selection in the aqueous solution, typically can be 20-40 weight %.
In step (2), HTS is the total of a class zeolite of a part of silicon atom in titanium atom substitution lattice framework Claim, chemical formula xTiO can be used2·SiO2Represent.The present invention is not limited especially for the content of titanium atom in HTS It is fixed, can be the conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, it is more excellent Elect 0.015-0.025 as.
The HTS can be the common HTS with various topological structures, for example：The titanium silicon point Son sieve can for the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, The HTS (such as Ti-Beta) of BEA structures, the HTS (such as Ti-MCM-22) of MWW structures, six sides The HTS (such as Ti-MCM-41, Ti-SBA-15) of structure, the HTS (such as Ti-MOR) of MOR structures, One in the HTS (such as Ti-TUN) of TUN structures and the HTS (such as Ti-ZSM-48) of other structures Plant or two or more.
Preferably, the HTS be the HTS selected from MFI structure, the HTS of MEL structures, It is more than one or both of the HTS of BEA structures and the HTS of hexagonal structure.It is highly preferred that described HTS is the HTS of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow HTS.It is described Hollow HTS is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the hollow knot The radical length of the chamber portion of structure is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time It is at least 70 milligrams per grams, the suction of the nitrogen absorption under low temperature of the HTS for the benzene adsorbance that is measured under conditions of 1 hour There is hysteresis loop between attached thermoisopleth and desorption isotherm.The hollow HTS is commercially available (such as commercially available The molecular sieve for being HTS from the trade mark of Hunan Jianchang Petrochemical Co., Ltd), can also be according to public in CN1132699C The method opened is prepared.
The method according to the invention, when the HTS uses template in preparation process, the HTS Can be the HTS that experienced the process (e.g., roasting process) for removed template method, or do not undergo Can also be both mixtures for the HTS of the process of removed template method.
The method according to the invention, at least part HTS is titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 Surface silicon titanium ratio be not less than body phase silicon titanium ratio, can so obtain the catalytic performance further improved, particularly can substantially prolong The single trip use life-span of long HTS.Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2 More than.It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5.It is further preferred that institute State surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that the table Face silicon titanium than with the body phase silicon titanium than ratio be 2-3, such as 2.2-2.8.The silicon titanium is than referring to silica and titanium oxide Mol ratio, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio is glimmering using X-ray Light spectrographic determination.
The method according to the invention, from the further catalytic performance for improving HTS, extends the angle of its service life Set out, at least part HTS is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is using including following step It is prepared by rapid method：
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained To dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N Meter is (in alkali source template Nitrogen element, in terms of N；In alkali source template not Nitrogen element, with OH-Meter)；
(B) alternatively, the dispersion liquid is stood into 6-24h at 15-60 DEG C；
(C) dispersion liquid that the dispersion liquid or step (B) obtained step (A) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3), the stage (1) was small in 80-150 DEG C of crystallization 6-72 to carry out crystallization When (h), the stage (2) is cooled to after not higher than 70 DEG C and residence time at least 0.5h, and the stage (3) is warming up to 120-200 DEG C Crystallization 6-96h again.
The alkali source template can be various templates usually used during synthesis of titanium silicon molecular sieve, for example：Institute It can be more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine to state alkali source template.The quaternary ammonium base Can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl The compound formed after (such as alkyl) substitution, the aliphatic hydramine can be various NH3In at least one hydrogen by containing The compound formed after aliphatic group (such as alkyl) substitution of hydroxyl.
Specifically, the alkali source template can represent for the quaternary ammonium base that is represented selected from Formulas I, Formula II aliphatic amine and formula It is more than one or both of aliphatic hydramine that III is represented.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4's Branched alkyl, R1、R2、R3And R4Instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, Normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R5(NH2)n(Formula II)
In Formula II, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl And C3-C6Branched alkyl, its instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, just Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.N is 2 When, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation Methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl can be included but is not limited to.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub And C3-C4Branched alkylidene, its instantiation can include but is not limited to methylene, ethylidene, sub- n-propyl and it is sub- just Butyl；M is 1,2 or 3.
The instantiation of the alkali source template can include but is not limited to：TMAH, tetraethyl ammonium hydroxide, TPAOH (includes the various isomers of TPAOH, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), TBAH (include the various isomers of TBAH, such as 4-n-butyl ammonium hydroxide With four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, It is more than one or both of diethanol amine and triethanolamine.Preferably, the alkali source template be tetraethyl ammonium hydroxide, It is more than one or both of TPAOH and TBAH.It is highly preferred that the alkali source template is TPAOH.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can be with For TiCl4、Ti(SO4)2And TiOCl2One or both of more than；The organic titanate can be general formula R7 4TiO4 The compound of expression, wherein, R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, Such as butyl titanate.
The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox2Quality hundred It can be more than 10%, preferably more than 15%, more preferably more than 20% to divide content.It is preferable to carry out preparing according to this During the HTS of mode, without using organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is preferably 100：(1-6)：(8-25)： (200-1500), more preferably 100：(2-5)：(10-20)：(400-1000).
The dispersion liquid that step (A) is obtained, which can be sent directly into step (C), carries out crystallization.Preferably, by step (A) 6-24h is stood at a temperature of 15-60 DEG C in obtained dispersion liquid feeding step (B).In step (A) and step (C) Between carry out step (B) the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 finally prepared can be significantly improved so that final system The surface silicon titanium ratio of standby HTS is not less than body phase silicon titanium ratio, can so significantly improve the titanium silicon molecule finally prepared The catalytic performance of sieve, particularly extends its single trip use life-span.Usually, by step (A) and step (C) it Between setting steps (B), the surface silicon titanium of the HTS finally prepared than with body phase silicon titanium than ratio can be in 1.2-5 In the range of, preferably in the range of 1.5-4.5 (such as in the range of 2.2-4.5), more preferably in the range of 2-3 (such as In the range of 2.2-2.8).The standing is carried out more preferably at a temperature of 20-50 DEG C, is entered at a temperature of such as 25-45 DEG C OK.
In step (B), when being stood, dispersion liquid can be placed in sealing container, unlimited appearance can also be placed in Stood in device.Preferably, step (B) is carried out in sealing container, can so avoid during standing to point Foreign matter is introduced into dispersion liquid or causes moieties volatilization in dispersion liquid to be lost in., can after the completion of step (B) described standing Crystallization is carried out directly to send into the dispersion liquid through standing in reactor, the dispersion liquid through standing redisperse can also be subjected to Crystallization is carried out in feeding reactor afterwards, preferably carries out sending into reactor after redisperse, so can further improve progress brilliant The dispersing uniformity of the dispersion liquid of change.The method of the redisperse can be conventional method, for example stirring, it is ultrasonically treated and Combination more than one or both of vibration.The duration of the redisperse is can make the dispersion liquid through standing be formed Even dispersion liquid is defined, and typically can be 0.1-12h, such as 0.5-2h.The redisperse can be carried out at ambient temperature, As carried out at a temperature of 15-40 DEG C.
In step (C), temperature is adjusted can be according to specific use to the heating rate of each phase temperature and rate of temperature fall The type of crystallization device selected, be not particularly limited.In general, temperature is increased into stage (1) crystallization The heating rate of temperature can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the stage (1) temperature to stage (2) temperature rate of temperature fall can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably For 5-10 DEG C/min.Can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, preferably For 2-40 DEG C/min, more preferably 5-20 DEG C/min.
In step (C), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, enters one Step is preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.Stage (2) Temperature is preferably not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.Stage (3) Crystallization temperature be preferably 140-180 DEG C, more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20h, More preferably 12-16h.
In step (C), in a preferred embodiment, the crystallization temperature in stage (1) is less than the stage (3) Crystallization temperature, so can further improve the catalytic performance of the HTS of preparation.Preferably, the crystallization in stage (1) Temperature is lower 10-50 DEG C than the crystallization temperature in stage (3).It is highly preferred that the crystallization temperature in stage (1) is than stage (3) Crystallization temperature it is low 20-40 DEG C.In step (C), in another preferred embodiment, during the crystallization in stage (1) Between be less than the stage (3) crystallization time, so can further improve the catalytic performance of the HTS finally prepared.It is excellent Selection of land, the short 5-24h of crystallization time of the crystallization time in stage (1) than the stage (3).It is highly preferred that the stage (1) Crystallization time is than the short 6-12h of crystallization time in stage (3), such as short 6-8h.In step (C), both preferred realities The mode of applying be may be used alone, can also be used in combination, and preferred compositions are used, i.e. the crystalline substance in stage (1) and stage (3) Change temperature and crystallization time meets the requirement of both preferred embodiments simultaneously.
In step (C), another preferred embodiment in, the temperature in stage (2) is not higher than 50 DEG C, and Residence time is at least 0.5h, such as 0.5-6h, so can further improve the catalytic performance of the HTS finally prepared. Preferably, the residence time in stage (2) is at least 1h, such as 1-5h.This preferred embodiment can be with foregoing two kinds Preferred embodiment it is used separately, can also be applied in combination, preferred compositions are used, be i.e. stage (1) and stage (3) Crystallization temperature and the temperature and residence time in crystallization time and stage (2) simultaneously meet above-mentioned three kinds of preferred embodiments Requirement.
HTS is reclaimed in the mixture that can be obtained using conventional method from step (C) crystallization.Specifically, may be used After alternatively being filtered and washed with the mixture for obtaining step (C) crystallization, solid matter is dried and is calcined, So as to obtain HTS.The drying and the roasting can be carried out under normal conditions.Usually, the drying Can be in environment temperature (such as 15 DEG C) to carrying out at a temperature of 200 DEG C.The drying can be in environmental pressure (generally 1 Standard atmospheric pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to drying Temperature and pressure and the mode of drying selected, be not particularly limited.For example, the drying is under ambient pressure During progress, temperature is preferably 80-150 DEG C, more preferably 100-120 DEG C, and the dry duration is preferably 0.5-5h, more Preferably 1-3h.The roasting can be carried out at a temperature of 300-800 DEG C, be carried out preferably at a temperature of 500-700 DEG C, Carry out, carried out further preferably at a temperature of 550-600 DEG C more preferably at a temperature of 550-650 DEG C.The roasting Duration can select according to the temperature being calcined, and typically can be 2-12h, preferably 2-5h.The roasting is preferred Carried out in air atmosphere.
The method according to the invention, at least part HTS is preferably modified processing before for step (2). The modification comprises the following steps：Using as the HTS of raw material with containing nitric acid (that is, HNO3) and at least A kind of modification liquid contact of peroxide.Refer to the titanium silicon point as the raw material of modification as the HTS of raw material Son sieve, can be the HTS without going through the modification, or live through the modification still Need to carry out the HTS of the modification again.In the present invention, the titanium silicon point of above-mentioned modification will be lived through Son sieve is referred to as modified HTS, and the HTS that above-mentioned modification is not lived through is referred to as into unmodified titanium silicon Molecular sieve.In step (2), can whole HTSs live through above-mentioned modification, or modified titanium The mixture of si molecular sieves and unmodified HTS.Usually, with the total of HTS described in step (2) On the basis of amount, at least more than 50 weight % HTS lives through the modification, more preferably at least 60 weight % HTS above lives through the modification.
In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, TBHP, peroxide Change hydrogen isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxygen Agent is hydrogen peroxide.The hydrogen peroxide can be the hydrogen peroxide existed in a variety of manners commonly used in the art.
Can be 1 as the HTS of raw material and the mol ratio of the peroxide in the modification： 0.01-5, preferably 1：0.05-2, more preferably 1：0.1-1.The consumption of the nitric acid can be according to the peroxide Consumption is selected.Usually, the mol ratio of the peroxide and the nitric acid can be 1：0.01-50, preferably 1： 0.1-20, more preferably 1：0.2-10, more preferably 1：0.5-5, particularly preferably 1：0.6-3.5, such as 1：0.7-3, The HTS is in terms of silica.
In the modification liquid, the concentration of peroxide and nitric acid can be each 0.1-50 weight %.Improved most from further The angle of the catalytic performance of the HTS of the modification prepared eventually is set out, preferably 0.5-25 weight %.It is highly preferred that In the modification liquid, the concentration of peroxide and nitric acid is respectively 1-15 weight %, such as 2-10 weight %.In one kind implementation In mode, the concentration of peroxide is 2-10 weight % (such as 2-8 weight %), and the concentration of nitric acid is 8-12 weight %.
The solvent of the modification liquid various can simultaneously dissolve the solvent of nitric acid and the peroxide to be common.It is preferred that Ground, the solvent of the modification liquid is water.
In the modification, it can be carried out as the HTS and modification liquid of raw material at a temperature of 10-350 DEG C Contact.From the angle of the catalytic performance for the HTS for further improving the modification finally prepared, the contact is excellent Contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that the contact is carried out at a temperature of 50-250 DEG C.Enter one Preferably, the contact is carried out step at a temperature of 60-200 DEG C.It is further preferred that the contact is at 70-180 DEG C At a temperature of carry out.The duration of the contact can be 1-10h, preferably 2-5h., will in the modification The pressure in container contacted as the HTS of raw material with the modification liquid can be selected according to Contact Temperature Select, can be environmental pressure, or pressurization.Usually, the HTS of raw material and the modification liquid will be used as The pressure in container contacted can be 0-5MPa, and the pressure is gauge pressure.Preferably, under pressure will Contacted as the HTS of raw material with the modification liquid.It is highly preferred that in closed container under self-generated pressure will make Contacted for the HTS of raw material with the modification liquid.
In the modification, as the HTS of raw material and the exposure level of the modification liquid preferably so that, with On the basis of the HTS of raw material, in ultraviolet-visible spectrum, modifying titanium-silicon molecular sieve is between 230-310nm Absworption peak peak area reduction by more than 2%, the pore volume of modifying titanium-silicon molecular sieve reduces more than 1%.Modifying titanium-silicon molecular sieve The peak area of absworption peak between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, further preferably 3-10% is reduced, 3-6% is still more preferably reduced.The pore volume of modifying titanium-silicon molecular sieve preferably reduces 1-20%, more preferably 1.5-10% is reduced, 2-5% is further preferably reduced.The pore volume is using static determination of nitrogen adsorption.
In the various commercial plants using HTS as catalyst, such as Ammoximation reaction device, hydroxylating In device and epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst declines, and needs Carry out in device or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to by catalyst from dress Drawn off in putting (that is, more catalyst changeout), and the current processing side of the catalyst (that is, drawing off agent or dead catalyst) drawn off Method is typically that accumulation is buried, and on the one hand occupies the land resource and inventory space of preciousness, the life of another aspect HTS Produce cost higher, directly pass into disuse and also result in great waste.The present inventor has found in research process, If these are drawn off after agent (that is, the HTS drawn off) is regenerated is used in step (2) as catalyst, Remain able to obtain higher thioether rate and desirable oxidation selectivity of product, while in continuous running for a long time, Show more preferable activity stability.Therefore, the method according to the invention, at least partly HTS is preferably The reaction unit (in addition to thioether oxidation unit) using HTS as catalyst through regeneration draws off agent.It is described to unload Agent can be drawn off for what is drawn off from the various reaction units for using HTS as catalyst by going out agent, for example, can be What is drawn off from oxidation reaction apparatus draws off agent.Specifically, it is described to draw off agent and draw off agent, hydroxyl for Ammoximation reaction device The one or more drawn off in agent for drawing off agent and epoxidation reaction device of glycosylation reaction device.More specifically, described unload Agent and propylene epoxy can be drawn off for the draw off agent, phenol hydroxylation reaction unit of cyclohexanone oxamidinating reaction unit by going out agent Change the one or more drawn off in agent of reaction unit.
The condition that agent regenerated will be drawn off to be not particularly limited, appropriate selection can be carried out according to the source for drawing off agent, For example：High-temperature roasting and/or solvent washing.
The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration can Think the 5-95% of activity (that is, the activity of fresh HTS) of the HTS when fresh.Preferably, The active 10-90% that the activity for drawing off agent through regeneration can be the HTS when fresh, more preferably exists Active 30-50% when fresh.It is that the HTS is active when fresh in the activity for drawing off agent through regeneration During 30-50%, in continuous running for a long time, more preferable activity stability is shown.It is further preferred that through Regeneration draws off the active 35-40% that the activity of agent is the HTS when fresh.The fresh HTS Activity generally more than 90%, usually more than 95%.
The activity is determined by the following method：Respectively agent and fresh HTS will be drawn off as cyclohexanone through regeneration The catalyst of Ammoximation reaction, the condition of the Ammoximation reaction is：HTS, 36 weight % ammoniacal liquor are (with NH3 Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone in mass ratio 1：7.5：10：7.5：10, At atmosheric pressure 2h is reacted in 80 DEG C.Calculate respectively using through regeneration when drawing off agent and fresh HTS as catalyst The conversion ratio of cyclohexanone, and using it as the activity for drawing off agent and fresh HTS through regeneration, wherein, ring Cyclohexanone that the conversion ratio of hexanone=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/is added rubs You measure] × 100%.
At least part HTS be the reaction unit through regeneration draw off agent when, using the total amount of the HTS as Benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 weight %.The method according to the invention, even if Whole HTSs are that the reaction unit through regeneration draws off agent (that is, the content for drawing off agent of the reaction unit through regeneration is 100 weight %) when, remain able to obtain higher thioether rate and desirable oxidation selectivity of product.
HTS in the method according to the invention, the HTS of the modification at least partly as raw material is special It is preferably above-mentioned to draw off agent through regeneration, the agent that draws off through regeneration is subjected to the modification, can further be improved The single trip use life-span of agent is drawn off through regeneration, and desirable oxidation selectivity of product can be significantly improved.
In the method according to the invention, step (2), the reactant mixture or step that step (1-1) can be obtained The mixture that (1-2) is obtained is mixed to form slurry with thioether and HTS, to carry out haptoreaction；Can also be by titanium Si molecular sieves are seated in the beds of fixed bed reactors, in step (2), can obtain step (1-1) Reactant mixture or the obtained mixture of step (1-2) flow through beds, so as to carry out haptoreaction.
In step (2), the HTS can be the former powder of HTS, or shaping HTS, Preferably it is molded HTS.Shaping HTS is typically contained as the HTS of active component and as viscous The carrier of agent is tied, wherein, the content of HTS can be conventional selection.Usually, with the shaping titanium silicon molecule On the basis of the total amount of sieve, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, more preferably For 70-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, more preferably 10-30 Weight %.The carrier of the shaping HTS can be conventional selection, such as aluminum oxide and/or silica.Prepare described The method for being molded HTS is it is known in the art, being no longer described in detail herein.The particle of the shaping HTS Size is also not particularly limited, and appropriate selection can be carried out according to concrete shape.Usually, the shaping titanium silicon molecule The average grain diameter of sieve can be 4-10000 microns, preferably 5-5000 microns, more preferably 40-4000 microns, such as 100-2000 microns.The average grain diameter is volume average particle size, can be determined using laser particle analyzer.
In step (2), the HTS is as catalyst, and its consumption, can realize that catalysis is defined Selected with carrying out catalytic concrete mode according to HTS and the liquid material.For example：By titanium silicon Molecular sieve is mixed to form slurry with the liquid material, so that when carrying out haptoreaction, the weight of thioether and HTS Than that can be 0.01-100：1, preferably 1-50：1, more preferably 10-30：1；In HTS and the liquid When the contact of material is carried out in fixed bed reactors, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-100h-1, preferably 1-80h-1, More preferably 10-60h-1, such as 20-40h-1.In the present invention, weight (hourly) space velocity (WHSV) is with whole HTSs in beds On the basis of.
The method according to the invention, beds can only load HTS, can also containing HTS and Inactive filler.Inactive filler is loaded in beds to be carried out to the amount of HTS in beds Adjustment, so that the speed to reaction is adjusted.When beds contain HTS and inactive filler, urge The content of inactive filler can be 5-95 weight % in agent bed.The inactive filler refers to do not have to oxidation reaction Or the basic filler without catalytic activity, its instantiation can include but is not limited to：Quartz sand, ceramic ring and ceramics are broken One or more in piece.
In step (2), tert-butyl hydroperoxide in the reactant mixture that the consumption of thioether can be obtained according to step (1-1) The content of TBHP is selected in the reactant mixture that hydrogen or step (1-2) are obtained.Usually, thioether Mol ratio with TBHP can be 1：0.1-10, preferably 1：0.2-5.Furthermore it is also possible to according to expection Desirable oxidation product the mol ratio of thioether and TBHP is optimized.For example, being in desirable oxidation product During sulfoxide (such as dimethyl sulfoxide (DMSO)), the mol ratio of thioether and TBHP is preferably 1：0.1-2, such as 1：0.5-1.5.
The method according to the invention, the thioether can be the various compounds containing-S- keys, and the thioether is preferably selected from carbon Atomicity is 2-18 thioether, such as dimethyl sulfide and/or thioanisole.
In step (2), mixture and thioether that the reactant mixture or step (1-2) that step (1-1) is obtained are obtained Contact with HTS is carried out under conditions of being enough sulfide oxidation.Usually, can 0-120 DEG C, preferably The reactant mixture or step (1-2) for obtaining step (1-1) at a temperature of 20-110 DEG C, more preferably 30-90 DEG C The mixture arrived and thioether and HTS haptoreaction.It is dimethyl sulfide in the thioether and desirable oxidation product is During dimethyl sulfoxide (DMSO), preferably at 20-60 DEG C, more preferably at 30-50 DEG C, further preferably at a temperature of 35-45 DEG C by step Suddenly the mixture that the reactant mixture or step (1-2) that (1-1) is obtained are obtained and thioether and HTS haptoreaction. The pressure in reactor contacted can be in the range of 0-5MPa, preferably in the range of 0.1-3.5MPa, institute Pressure is stated in terms of gauge pressure.
The method according to the invention, the reactant mixture that step (2) is obtained contains the desirable oxidation production of sulfide oxidation formation Thing (such as sulfoxide), can be separated using conventional method to it, so that desirable oxidation product (such as sulfoxide) is obtained, point The unreacted reactant separated out can be recycled.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, agents useful for same is commercial reagent, and pressure is gauge pressure.
In following examples and comparative example, the content of each composition in the reaction solution obtained using gas chromatography analysis, herein On the basis of below equation is respectively adopted calculate thioether rate and sulfoxide selectivity.
XThioether=[(mo Thioether- mThioether)/mo Thioether] × 100%
Wherein, XThioetherRepresent thioether rate；
mo ThioetherRepresent the mole of thioether added；
mThioetherRepresent the mole of unreacted thioether.
SSulfoxide=[nSulfoxide/(no Thioether- nThioether)] × 100%
Wherein, SSulfoxideRepresent sulfoxide selectivity；
no ThioetherRepresent the mole of thioether added；
nThioetherRepresent the mole of unreacted thioether；
nSulfoxideRepresent the mole of the sulfoxide of reaction generation.
In following examples and comparative example, static nitrogen adsorption method is respectively adopted and solid ultraviolet-visible diffuses spectrometry to changing The pore volume and ultraviolet absorption peak of the HTS of property before and after the processing are characterized, wherein, solid ultraviolet-visible diffuses (UV-Vis) analysis is composed to carry out on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；Static N2 adsorption test Carried out on the static n2 absorption apparatus of the types of ASAP 2405 of Micromeritics companies.
It is related to drawing off in the embodiment and comparative example of agent through regeneration below, HTS (bag is determined using following methods Include regenerative agent and fresh dose) activity：By HTS, 36 weight % ammoniacal liquor (with NH3Meter), 30 weight % Hydrogen peroxide (with H2O2Meter), the tert-butyl alcohol and cyclohexanone be by weight=1：7.5：10：7.5：In air after 10 mixing In after 80 DEG C of stirring reactions 2 hours under pressure, reactant is filtered, liquid phase analyzed with gas-chromatography, use with Lower formula calculates the conversion ratio of cyclohexanone and as the activity of HTS,
The conversion ratio of cyclohexanone=[(mole of the cyclohexanone of addition-unreacted cyclohexanone mole)/ring added The mole of hexanone] × 100%.
In embodiment and comparative example included below the step of prepare HTS, X-ray diffraction is analyzed in Siemens On D5005 type X-ray diffractometers carry out, using sample and authentic specimen between 2 θ is 22.5 ° -25.0 ° the five fingers diffractive features The ratio of diffracted intensity (peak height) sum at peak represents crystallinity of the sample relative to authentic specimen；Fourier transform is red External spectrum analysis is carried out on the type Fourier transformation infrared spectrometers of Nicolet 8210；Silicon titanium ratio refers to silica and titanium oxide Mol ratio, surface silicon titanium is than the ESCALab250 type x-ray photoelectron power spectrums using Thermo Scientific companies Instrument is determined, and body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.
Embodiment 1-20 is used for the method for illustrating the present invention.
Embodiment 1
(1-1) is 120 DEG C in temperature by the tert-butyl alcohol and oxygen and pressure is haptoreaction under conditions of 2MPa, is contained There is the reactant mixture of TBHP, the composition of the reactant mixture is analyzed with gas-chromatography, uncle is determined The content of butylhydroperoxide is 40 weight %.Wherein, the mol ratio of the tert-butyl alcohol and oxygen is 1：2；Oxygen is with oxygenous The form of body is provided, in oxygen-containing gas, and the content of oxygen is 80 volume %, and the content of nitrogen is 20 volume %.
The reactant mixture that (1-2) obtains step (1-1) is with hydrochloric acid (HCl concentration is 36.5 weight %) in high pressure Mixed in reactor, wherein, TBHP and HCl mol ratio in the reactant mixture that step (1-1) is obtained For 1：0.005, by the temperature control in autoclave be 30 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 4h.
(2) titanium-silicon molecular sieve TS-1 is with reference to Zeolites, 1992, the Vol.12 method system described in the 943-950 pages Standby, specific method is as follows.At room temperature (20 DEG C), 22.5g tetraethyl orthosilicates and 7.0g are regard as the 4 third of template Base ammonium hydroxide is mixed, and adds 59.8g distilled water, and stirring mixing is hydrolyzed after normal pressure (1 standard atmospheric pressure) and 60 DEG C 1.0h, obtains the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, be slowly added into the hydrating solution by The solution that 1.1g butyl titanates are constituted with 5.0g anhydrous isopropyl alcohols, stirs 3h at 75 DEG C by gained mixture, obtains clear Clear transparent colloid.This colloid is placed in stainless steel sealing reactor, constant temperature places 36h at a temperature of 170 DEG C, obtains The mixture of crystallization product.The filtering of obtained mixture is collected after obtained solid matter water used wash, it is dry in 110 DEG C Dry 1h, is then calcined 6h at 500 DEG C, so as to obtain titanium-silicon molecular sieve TS-1, its titanium oxide content is 2.8 weight %.
The reactant mixture that step (1-2) is obtained is placed in autoclave with dimethyl sulfide and titanium-silicon molecular sieve TS-1 In, it is stirred reaction.Wherein, the weight ratio of dimethyl sulfide and HTS is 15：1, step (1-2) To reactant mixture in TBHP and dimethyl sulfide mol ratio be 1.2：1, by autoclave Temperature control be 35 DEG C, by Stress control be 1MPa.React after 2h, stop reaction, will be anti-in autoclave Answer mixture to be filtered, obtain liquid phase and the HTS reclaimed, analyze the composition of obtained liquid phase, calculate diformazan Base thioether rate and dimethyl sulfoxide (DMSO) selectivity, recycling in step (2) is re-fed into by the HTS of recovery. The 1st use of titanium-silicon molecular sieve TS-1 and reaction result when using for the 45th time are listed in table 1.
Embodiment 2
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, without step (1-2), step Suddenly the reactant mixture that (1-1) is obtained is sent directly into step (2).
Experimental result is listed in table 1.
Embodiment 3
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), titanium silicon point Son sieve TS-1 is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：4： 12：400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 24h is stood in room temperature (being 25 DEG C, similarly hereinafter) after being sealed using sealed membrane, 2h is stirred at 35 DEG C followed by magnetic agitation, It is allowed to disperse again.Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization is undergone at 140 DEG C 6h, is then cooled to 30 DEG C of experience second stage by mixture and stops after 2h, continue in sealing reactor in 170 DEG C At a temperature of experience phase III crystallization 12h (wherein, be by the heating rate of room temperature to first stage crystallization temperature 2 DEG C/min, be 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second segment treatment temperature, by second stage Manage temperature to phase III crystallization temperature heating rate be 10 DEG C/min), by gained crystallization product take out after without filtering and Washing step, directly dries 2h in 110 DEG C, and 3h is then calcined at 550 DEG C, obtains molecular sieve.The XRD of gained sample Crystalline phase figure is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), and illustrate to obtain is with MFI structure Titanium-silicon molecular sieve TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak, show titanium Into framework of molecular sieve, in the HTS, titanium oxide content is 3.5 weight %, surface silicon titanium ratio/body phase silicon titanium ratio For 2.58, (in HTS prepared by embodiment 1,1.05) surface silicon titanium ratio/body phase silicon titanium ratio is.
Experimental result is listed in table 1.
Embodiment 4
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing During titanium-silicon molecular sieve TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phases figure of gained sample is with implementing Titanium-silicon molecular sieve TS-1 prepared by the step of example 1 (2) is consistent, and illustrate to obtain is the TS-1 molecules with MFI structure Sieve；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, should In HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.
Experimental result is listed in table 1.
Embodiment 5
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing During titanium-silicon molecular sieve TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phases figure of gained sample and embodiment 1 Titanium-silicon molecular sieve TS-1 prepared by step (2) is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure； In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the titanium silicon In molecular sieve, surface silicon titanium ratio/body phase silicon titanium ratio is 2.37, and titanium oxide content is 3.2 weight %.
Experimental result is listed in table 1.
Embodiment 6
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), the first rank The crystallization time of section is 12h.The HTS that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1 Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio For 3.78, titanium oxide content is 3.4 weight %.
Experimental result is listed in table 1.
Embodiment 7
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), second-order Section is to be cooled to 70 DEG C of stop 2h.The titanium silicon molecule that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Sieve that TS-1 is consistent, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 2.75, and titanium oxide content is 3.1 weight %.
Experimental result is listed in table 1.
Embodiment 8
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), second-order Section is to be cooled to 30 DEG C of stop 0.2h.The titanium silicon point that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Son sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 1.14, and titanium oxide content is 2.4 weight %.
Experimental result is listed in table 1.
Embodiment 9
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), without Second stage.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), Illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby occur Absworption peak, shows that titanium has been enter into framework of molecular sieve, in the HTS, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.08, Titanium oxide content is 2.5 weight %.
Experimental result is listed in table 1.
Embodiment 10
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), prepare titanium During silicalite TS-1, aqueous dispersions do not stand 24h at room temperature, but are sent directly into reactor and carry out crystallization.Institute Sample XRD crystalline phases figure it is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), illustrate to obtain is TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show Titanium has been enter into framework of molecular sieve, in the HTS, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.18, and titanium oxide content is 3.5 weight %.
Experimental result is listed in table 1.
Embodiment 11
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), titanium silicon point Son sieve TS-1 is modified processing before as catalyst using following methods：The titanium silicon point of the preparation of raw material will be used as Son sieve TS-1 is with containing HNO3(HNO3Mass concentration 10%) and the hydrogen peroxide (mass concentration of hydrogen peroxide for For 7.5%) the aqueous solution mixing, by obtained mixture in closed container in 70 DEG C of stirring reaction 5h, what is obtained is anti- Answer the temperature of mixture to be down to after room temperature to be filtered, obtained solid matter is dried to constant weight at 120 DEG C, is modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2The mol ratio of meter, HTS and hydrogen peroxide is 1： 0.1.Compared with raw material HTS, in 230-310nm in the UV-Vis spectrum of the HTS of obtained modification Between absworption peak peak area reduce 3.5%, by static determination of nitrogen adsorption pore volume reduce 2.6%.
Experimental result is listed in table 1.
Embodiment 12
Dimethyl sulfide is aoxidized using with the identical method of embodiment 11, unlike, in modification, it is used as original What is expected is titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 of being drawn off from phenol hydroxylation reaction unit through regeneration Using with the step of embodiment 1 (2) identical method prepare, the titanium-silicon molecular sieve TS-1 drawn off at a temperature of 570 DEG C in 5h is calcined in air atmosphere and is regenerated, the activity after regeneration is 35%, and 96%) activity when fresh is.With raw material titanium silicon Molecular sieve is compared, the peak of the absworption peak in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm Area reduces 3.3%, and 2.8% is reduced by the pore volume of static determination of nitrogen adsorption.
Experimental result is listed in table 1.
Embodiment 13
Dimethyl sulfide is aoxidized using with the identical method of embodiment 12, unlike, it will directly make in embodiment 12 It is used as catalyst for the titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit through regeneration of raw material, i.e., does not enter Row modification.
Experimental result is listed in table 1.
Comparative example 1
Dimethyl sulfide is aoxidized using with the step of embodiment 1 (2) identical method, unlike, without step (1-1) and step (1-2), in step (2) using TBHP t-butanol solution (in the t-butanol solution, TBHP in the reactant mixture that the concentration of TBHP is obtained with the step of embodiment 1 (1) it is dense Degree is identical) replace step (1-2) obtained reactant mixture.
Experimental result is listed in table 1.
Comparative example 2
Dimethyl sulfide is aoxidized using with the step of embodiment 1 (2) identical method, unlike, with hydrogen peroxide (mistake The concentration of hydrogen oxide is 25 weight %) replace the reactant mixture that step (1-2) is obtained in embodiment 1.
Experimental result is listed in table 1.
Table 1
Embodiment 14
(1-1) is by the tert-butyl alcohol and TBHP with oxygen in the condition that temperature is 100 DEG C and pressure is 1.2MPa Lower haptoreaction, obtains the reactant mixture containing TBHP, with group of the gas-chromatography to the reactant mixture Into being analyzed, the content for determining TBHP is 30 weight %.Wherein, the mol ratio of the tert-butyl alcohol and oxygen is 1：2, the mol ratio of TBHP and the tert-butyl alcohol is 0.003：1；Oxygen is provided in the form of oxygen-containing gas, is contained In carrier of oxygen, the content of oxygen is 90 volume %, and the content of nitrogen is 10 volume %.
The reactant mixture that (1-2) obtains step (1-1) is with hydrobromic acid (HBr concentration is 30 weight %) in high pressure Mixed in reactor, wherein, TBHP and HBr mol ratio in the reactant mixture that step (1-1) is obtained For 1：0.001, by the temperature control in autoclave be 35 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 3h.
(2) as raw material HTS be purchased from Hunan Jianchang Petrochemical Co., Ltd the trade mark be HTS sky Heart HTS, its titanium oxide content is 2.5 weight %.
By hollow HTS with containing HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxidating for The mass concentration of hydrogen for 5%) the aqueous solution mixing, by obtained mixture in closed container under 120 DEG C of pressure itselfs Stirring reaction 4h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter 120 DEG C dry to constant weight, obtain modified HTS.Wherein, hollow HTS is with SiO2Meter, HTS Mol ratio with hydrogen peroxide is 1：0.4.Compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 4.6%, by the hole of static determination of nitrogen adsorption Hold and reduce 3.8%.
By the mixture of modified hollow HTS and non-modified hollow HTS (with the total of the mixture On the basis of amount, the content of modified hollow HTS is 60 weight %) it is seated in micro fixed-bed reactor, shape Into beds.The reactant mixture and dimethyl sulfide that step (1-2) is obtained are from the entrance positioned at reactor bottom Send into reactor, flow through beds.Wherein, the tert-butyl hydroperoxide in the reactant mixture that step (1) is obtained The mol ratio of hydrogen and dimethyl sulfide is 1：2, it is 40 DEG C by the temperature control in beds, by the pressure in reactor Power control is 1.2MPa, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 40h-1。
The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 630h and listed in table 2.
Embodiment 15
Using with the identical method cacodyl oxide base thioether of embodiment 14, unlike, what is loaded in beds is The hollow HTS of non-modified processing (is used as the hollow HTS of raw material with the step of embodiment 14 (2) Source is identical).
The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 450h and listed in table 2.
Embodiment 16
Using with the identical method cacodyl oxide base thioether of embodiment 14, unlike, prepare modified HTS When the raw material that uses be being drawn off from cyclohexanone oxamidinating reaction unit through regeneration hollow HTS (hollow titanium Si molecular sieves and the step of embodiment 14 (2) identical, the hollow titanium drawn off as the source of the hollow HTS of raw material Si molecular sieves are calcined 6h in air atmosphere at a temperature of 550 DEG C and regenerated, and the activity after regeneration is 40%, when fresh Activity for 97%).Compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification The peak area of absworption peak between 230-310nm reduces 4.8%, and 3.5% is reduced by the pore volume of static determination of nitrogen adsorption.
The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 750h and listed in table 2.
Embodiment 17
(1-1) is 120 DEG C in temperature by the tert-butyl alcohol and oxygen and pressure is haptoreaction under conditions of 2MPa, is contained There is the reactant mixture of TBHP, the composition of the reactant mixture is analyzed with gas-chromatography, uncle is determined The content of butylhydroperoxide is 25 weight %.Wherein, the mol ratio of the tert-butyl alcohol and oxygen is 1：3；Oxygen is with oxygenous The form of body is provided, in oxygen-containing gas, and the content of oxygen is 80 volume %, and the content of nitrogen is 20 volume %.
The reactant mixture that (1-2) obtains step (1-1) and hydrochloric acid (HCl concentration is 25 weight %) are anti-in high pressure Answer in kettle and mix, wherein, TBHP and HCl mol ratio are in the reactant mixture that step (1-1) is obtained 1：0.01, it is normal pressure (that is, 1 by the Stress control in autoclave by 40 DEG C of temperature control in autoclave Standard atmospheric pressure), incorporation time is 2h.
(2) titanium-silicon molecular sieve TS-1 used in this step is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：2： 10：600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 10h is stood at 40 DEG C after being sealed using sealed membrane, 0.5h is stirred at 25 DEG C followed by magnetic agitation, is allowed to again It is scattered.Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization 8h is undergone at 130 DEG C, connects And mixture is cooled to after 50 DEG C of experience second stage stop 5h, continue the temperature in 170 DEG C in sealing reactor and pass through Go through phase III crystallization 16h (wherein, by room temperature to first stage crystallization temperature heating rate be 1 DEG C/min, by First stage crystallization temperature to second stage treatment temperature rate of temperature fall be 10 DEG C/min, by second stage treatment temperature to The heating rate of phase III crystallization temperature is 20 DEG C/min), without filtering and purge step after gained crystallization product is taken out Suddenly, 3h directly is dried in 120 DEG C, 2h is then calcined at 580 DEG C, obtain molecular sieve.The XRD crystalline phases of gained sample Figure is consistent with the titanium-silicon molecular sieve TS-1 of the step of embodiment 1 (2) preparation, and illustrate to obtain is the titanium with MFI structure Silicalite TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak, show that titanium has been enter into In framework of molecular sieve, the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.25, and titanium oxide content is 2.6 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, beds are formed.By step The reactant mixture and dimethyl sulfide that (1-2) is obtained flow through and urged from positioned at the entrance of reactor bottom feeding reactor Agent bed.Wherein, TBHP and dimethyl sulfide in the reactant mixture that step (1-1) is obtained rub You are than being 1：3, it is 50 DEG C by the temperature control in beds, is 0.8MPa by the Stress control in reactor,
The weight (hourly) space velocity (WHSV) of dimethyl sulfide is 40h-1。
The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 590h and listed in table 2.
Table 2
Embodiment 18
(1-1) is 120 DEG C in temperature by the tert-butyl alcohol and oxygen and pressure is haptoreaction under conditions of 1.8MPa, obtains Reactant mixture containing TBHP, is analyzed the composition of the reactant mixture with gas-chromatography, it is determined that The content of TBHP is 45 weight %.Wherein, the mol ratio of the tert-butyl alcohol and oxygen is 1：1.5；Oxygen with containing The form of carrier of oxygen is provided, in oxygen-containing gas, and the content of oxygen is 85 volume %, and the content of argon gas is 15 volume %.
The reactant mixture that (1-2) obtains step (1-1) and hydrochloric acid (HCl concentration is 20 weight %) are anti-in high pressure Answer in kettle and mix, wherein, TBHP and HCl mol ratio are in the reactant mixture that step (1-1) is obtained 1：0.001, by the temperature control in autoclave be 35 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 4h.
(2) titanium-silicon molecular sieve TS-1 that this step is used is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：5： 18：1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker After middle utilization sealed membrane sealing 8h is stood at 45 DEG C；Dispersion liquid through standing is transferred in sealing reactor, at 140 DEG C First stage crystallization 6h is undergone, mixture then is cooled into 40 DEG C of experience second stage stops after 1h, continues in sealing Phase III crystallization 12h is undergone (wherein, by room temperature to first stage crystallization temperature at a temperature of 160 DEG C in reactor The heating rate of degree is 5 DEG C/min, is to the rate of temperature fall of second stage treatment temperature by first stage crystallization temperature 5 DEG C/min, be 5 DEG C/min by the heating rate of second stage treatment temperature to phase III crystallization temperature), by gained crystallization Without filtering and washing step after product taking-up, 2h directly are dried in 110 DEG C, then 3h are calcined at 550 DEG C, obtained Molecular sieve.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), says It is bright that obtain is the titanium-silicon molecular sieve TS-1 with MFI structure；In FFIR figure, in 960cm-1It is attached Closely there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.71, titanium oxide content is 4.3 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, beds are formed.By step The mixture and thioanisole that (1-2) is obtained flow through catalyst bed from positioned at the entrance of reactor bottom feeding reactor Layer.Wherein, the mol ratio of TBHP and thioanisole in the reactant mixture that step (1) is obtained is 1.2： 1, it is 85 DEG C by the temperature control in beds, is 2.5MPa by the Stress control in reactor, thioanisole Weight (hourly) space velocity (WHSV) is 20h-1。
The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 520h and listed in table 3.
Embodiment 19
Thioanisole is aoxidized using with the identical method of embodiment 18, unlike, the titanium-silicon molecular sieve TS-1 of preparation Before as catalyst, processing is modified using following methods.
By the titanium-silicon molecular sieve TS-1 of preparation with containing HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (mistake for The mass concentration of hydrogen oxide for 2%) the aqueous solution mixing, by obtained mixture in closed container under self-generated pressure 170 DEG C of stirring reaction 2.5h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter Dried at 120 DEG C to constant weight, obtain modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, titanium silicon The mol ratio of molecular sieve and hydrogen peroxide is 1：1.Through characterizing, compared with raw material HTS, the titanium of obtained modification The peak area of absworption peak in the UV-Vis spectrum of si molecular sieves between 230-310nm reduces 5.7%, is inhaled by static nitrogen The pore volume that attached method is determined reduces 4.1%.
The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 600h and listed in table 3.
Embodiment 20
Thioanisole is aoxidized using with the identical method of embodiment 19, unlike, raw material is used as in modification Be being drawn off from phenol hydroxylation reaction unit through regeneration titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 use with Prepared by the step of embodiment 18 (2) identical method, the titanium-silicon molecular sieve TS-1 drawn off is at a temperature of 580 DEG C in air 4h is calcined in atmosphere and is regenerated, the activity after regeneration is 40%, and 95%) activity when fresh is.With the titanium as raw material Si molecular sieves are compared, the absworption peak in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm Peak area reduces 5.5%, and 4.3% is reduced by the pore volume of static determination of nitrogen adsorption.
The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 720h and listed in table 3.
Table 3
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, can carry out a variety of simple variants to technical scheme, These simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not contradiction In the case of, it can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible combination no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to this hair Bright thought, it should equally be considered as content disclosed in this invention.

Claims (21)

1. a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step (1-2)：
In step (1-1), by the tert-butyl alcohol and oxygen haptoreaction, the catalytic condition causes haptoreaction to obtain Reactant mixture in TBHP content be more than 1 weight %；
In step (1-2), the reactant mixture that step (1-1) is obtained is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reactant mixture that will be obtained containing step (1-1) With the raw mixture and HTS haptoreaction of thioether, or the mixture and sulphur that will be obtained containing step (1-2) The raw mixture of ether and HTS haptoreaction.
2. according to the method described in claim 1, wherein, in step (1-1), the catalytic condition causes The total content of TBHP is 2-90 weight %, preferably 10-70 weights in the reactant mixture that haptoreaction is obtained Measure %, more preferably more preferably 15-60 weight %, 20-50 weight %；The content of the tert-butyl alcohol is 10-98 weight %, preferably 30-90 weight %, more preferably 40-85 weight %, more preferably 50-80 weight %.
3. method according to claim 1 or 2, wherein, in step (1-1), mole of the tert-butyl alcohol and oxygen Than for 1：0.01-20, preferably 1：0.1-10, more preferably 1：0.2-5, the haptoreaction is 70-160 in temperature DEG C, be preferably 90-140 DEG C, and pressure be 0-3MPa, be preferably 0.5-2.5MPa under conditions of carry out, the pressure Power is in terms of gauge pressure.
4. according to the method described in claim 1, wherein, in step (1-2), inorganic acid and TBHP Mol ratio be 0.00001-0.1：1, preferably 0.0001-0.05：1, more preferably 0.001-0.01：1.
5. according to the method described in claim 1, wherein, in step (1-2), the temperature that is blended in is 20-100 DEG C, be preferably 20-80 DEG C, more preferably 25-60 DEG C, and pressure be 0-2MPa under conditions of carry out, the pressure In terms of gauge pressure；The time of the mixing is 0.1-5 hours, preferably 0.5-4 hours, more preferably 2-4 hours.
6. the method according to any one in claim 1-5, wherein, in step (1-2), the inorganic acid For HCl and/or HBr.
7. the method according to any one in claim 1-6, wherein, in step (2), at least part titanium silicon Molecular sieve is the HTS of the modification of experience modification, and the modification is including will be used as the titanium silicon molecule of raw material Sieve is contacted with the modification liquid containing nitric acid and at least one peroxide.
8. method according to claim 7, wherein, in the modification, it is used as the titanium silicon molecule of raw material The mol ratio of sieve and the peroxide is 1：0.01-5, preferably 1：0.05-2, more preferably 1：0.1-1, the mistake The mol ratio of oxide and the nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, enters one Step is preferably 1：0.5-5, particularly preferably 1：0.6-3.5, the HTS is in terms of silica.
9. the method according to claim 7 or 8, wherein, in the modification liquid, peroxide and nitric acid it is dense Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-25 weight %, more preferably 1-15 weight %, 2-10 Weight %.
10. the method according to any one in claim 7-9, wherein, in the modification, it is used as original The HTS of material and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, it is further excellent Contacted at a temperature of selecting 60-200 DEG C, still more preferably 70-180 DEG C, the contact is 0-5MPa's in pressure Carried out in container, the pressure is gauge pressure；The time of the contact is 1-10 hours, preferably 2-5 hours.
11. method according to any one of claims of claim 7-10, wherein, in the modification liquid, the peroxidating Thing is selected from hydrogen peroxide, hydroperoxides and peracid, is preferably selected from hydrogen peroxide, TBHP, ethylbenzene peroxide Change hydrogen, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
12. the method according to any one in claim 7-11, wherein, in the modification, it is used as original The exposure level of the HTS of material and the modification liquid causes, using on the basis of the HTS as raw material, in purple In outside-visible spectrum, the peak area reduction by more than 2% of the absworption peak of modified HTS between 230-310nm, It is preferred that reducing 2-30%, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably reduces 3-6%, The pore volume of modified HTS reduces more than 1%, preferably reduces 1-20%, more preferably reduces 1.5-10%, further It is preferred that reducing 2-5%, the pore volume is using static determination of nitrogen adsorption.
13. the method according to any one in claim 1-12, wherein, in step (2), at least part titanium Si molecular sieves are titanium-silicon molecular sieve TS-1, and the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, institute Mol ratio of the silicon titanium than referring to silica and titanium oxide is stated, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, The body phase silicon titanium ratio uses x-ray fluorescence spectrometry；
Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2；
It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；
It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5；
It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 2-3.
14. the method according to claim 1-13, wherein, in step (2), at least part HTS is Titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 is prepared using the method comprised the following steps：
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained To dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N Meter；
(B) alternatively, the dispersion liquid is stood 6-24 hours at 15-60 DEG C；
(C) dispersion liquid that the dispersion liquid or step (B) obtained step (A) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3) to carry out crystallization, the stage (1) 80-150 DEG C, preferably 110-140 DEG C, More preferably at 120-140 DEG C, further preferably in 130-140 DEG C of crystallization 6-72 hours, preferably 6-8 hours；Stage (2) It is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably 1-5 hours；Stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96 hours, preferably 12-20 hours.
15. method according to claim 14, wherein, stage (1) and stage (3) are met in following condition One of or both：
Condition 1：The crystallization temperature in stage (1) is less than the crystallization temperature in stage (3), it is preferable that the crystalline substance in stage (1) Change temperature lower 10-50 DEG C than the crystallization temperature in stage (3), it is preferably low 20-40 DEG C；
Condition 2：The crystallization time in stage (1) is less than the crystallization time in stage (3), it is preferable that the crystalline substance in stage (1) The change time is shorter 5-24 hours than the crystallization time in stage (3), preferably short 6-12 hours.
16. the method according to claims 14 or 15, wherein, the stage (2) is cooled to not higher than 50 DEG C, and Residence time is at least 1 hour.
17. the method according to any one in claim 14-16, wherein, the titanium source be inorganic titanium salt and/ Or organic titanate；The alkali source template is more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine, Preferably quaternary ammonium base, more preferably TPAOH；The inorganic silicon source is silica gel and/or Ludox；
Preferably, the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2One or both of more than；It is described organic Titanate esters are selected from general formula R7 4TiO4The compound of expression, R7Selected from the alkyl with 2-4 carbon atom.
18. the method according to any one in claim 1-17, wherein, at least part HTS is derived from At least one reaction unit draws off agent, described to draw off agent and draw off agent, hydroxylating device for Ammoximation reaction device Draw off agent and epoxidation reaction device draw off agent.
19. the method according to any one in claim 1-18, wherein, the thioether be dimethyl sulfide and/ Or thioanisole.
20. the method according to any one in claim 1-19, wherein, in step (2), step (1-1) The mol ratio of TBHP and thioether in obtained reactant mixture is 0.1-10：1, preferably 0.1-2：1.
21. the method according to any one in claim 1-20, wherein, in step (2), the contact is anti- It should be 0-120 DEG C in temperature, be preferably 20-110 DEG C, be more preferably 30-90 DEG C, and pressure is 0-5MPa, is preferably Carried out under conditions of 0.1-3.5MPa, the pressure is in terms of gauge pressure.
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